Charge-transfer acceptor phases

The stetic parameter accounts for steric effects on the solvation of a-amino and carboxyl groups caused by the side chain. We have not attempted to account for any charge transfer interactions as none of the compounds studied is a very effective charge transfer acceptor, and the water and n-octanol phases can only function as change transfer donors. Further support is provided by the correlation of log P values for Ph(CH2)mX (m = 1, 2, 3) with the equation... 

Much of chemistry occurs in the condensed phase solution phase ET reactions have been a major focus for theory and experiment for the last 50 years. Experiments, and quantitative theories, have probed how reaction-free energy, solvent polarity, donor-acceptor distance, bridging stmctures, solvent relaxation, and vibronic coupling influence ET kinetics. Important connections have also been drawn between optical charge transfer transitions and thennal ET. 

Induction of chirality in No phases was also shown to be possible using charge transfer interactions, via jt-jt stacking. The binary mixture of mesogen 8, which is electron rich, with chiral electron-deficient molecule 9 was shown to induce a twist in the mesophase.15 Furthermore, nonmesogenic 8 gave rise to a cholesteric mesophase, denoted as being of the columnar type (N ), when present in a ternary system with TNF (trinitrofluorenone, an electron acceptor)... 

EA are the ionization potential and electron affinity of the donor anions and acceptor cations, respectively, in the gas phase and wp represents the ion-pair interaction. (Note the ionization potentials in the gas phase parallel the anodic potentials in solution for structurally related electron donors the same interrelationship applies to electron affinities and cathodic potentials.) Accordingly, these coloured crystals are also referred to as charge-transfer salts (Wei etal., 1992). 

It is impractical to measure the gas phase ionization potential for Fe(CNBF3)8-4. However, it is possible to obtain closely related information from charge-transfer spectra and oxidation potentials for Fephen2(CN)2and its adducts. Solvation effects maybe minimized by the determination of oxidation potentials in a solvent of relatively low dielectric constant. When methylene chloride is used as a solvent, the observed trends in oxidation potentials correlate well with expected acidity of the acceptor ... 

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